CN112625215B - Organic-inorganic hybrid intrinsic liquid crystal epoxy resin and preparation method and application thereof - Google Patents
Organic-inorganic hybrid intrinsic liquid crystal epoxy resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN112625215B CN112625215B CN202011470779.5A CN202011470779A CN112625215B CN 112625215 B CN112625215 B CN 112625215B CN 202011470779 A CN202011470779 A CN 202011470779A CN 112625215 B CN112625215 B CN 112625215B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- epoxy resin
- organic
- inorganic hybrid
- crystal epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides an organic-inorganic hybrid intrinsic liquid crystal epoxy resin and a preparation method and application thereof. The preparation method of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin firstly introduces Schiff base structural elements and then prepares the organic-inorganic hybrid intrinsic liquid crystal epoxy resin by a bisphenol-epichlorohydrin method. The heat conductivity coefficient of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin reaches 0.7-1.6W m ‑1 K ‑1 Compared with the common resin matrix, the heat conduction coefficient of the composite material is higher. The organic-inorganic hybrid intrinsic liquid crystal epoxy can be applied to the fields of electronic packaging materials, heat conduction materials and the like after being thermally cured.
Description
Technical Field
The invention belongs to the technical field of high-thermal-conductivity high polymer materials, and particularly relates to organic-inorganic hybrid intrinsic liquid crystal epoxy resin and a preparation method and application thereof.
Background
With rapid progress of science and technology, electronic equipment and devices are continuously developed towards light, thin, short and direction, so that the power is greatly increased when the electronic equipment and devices work, the dissipated power density per unit area is rapidly increased, and researches indicate that the dissipated power density of the current high-power electronic devices can reach 1000W cm when the electronic equipment and devices work -2 Thereby causing a serious heat dissipation problem. In addition, whether the heat dissipation problem can be effectively solved or not is a key factor for continuation of moore's law, and is a bottleneck for development of electronic devices. The ideal heat conducting material has the advantages of high heat conductivity, high insulation, excellent mechanical property, easy processing and forming and the like. Compared with traditional heat conducting materials such as inorganic materials, metal materials and the like, the polymer heat conducting materials and the excellent characteristics of good electrical insulation, corrosion resistance, excellent mechanical strength, low cost, easy processing and the like are widely applied to the field of heat conducting. At present, the research on polymer heat conduction materials mainly involves the following two aspects: the high heat-conducting polymer composite material is prepared by adding high heat-conducting particles and an intrinsic polymer with high heat-conducting property is synthesized. The high thermal conductive composite material is remarkably improved only when the content of the thermal conductive particles reaches a threshold value, but other excellent characteristics of the polymer, such as mechanics, electrical insulation and the like, are often sacrificed, and the thermal conductive performance of the high thermal conductive composite material is reduced due to the difference of the types, particle sizes and dispersivity of the thermal conductive particles. Therefore, the intrinsic type heat conductive polymer has received a great deal of attention, and it is far more effective to increase the thermal conductivity of the system by improving the thermal conductivity of the polymer continuous phase matrix than to increase the amount of the heat conductive particles. For example, chinese publications CN110229318A and CN109180979A disclose that the thermal conductivity of a polymer matrix is improved by introducing mesogens into the main chain and side chain of the polymer and by adjusting the microscopic degree of order of the polymer to form a regularly arranged mesomorphic structure.
However, in the prior art, the thermal conductivity of the material is not improved by constructing mesomorphic elements and inorganic nano particles to prepare organic-inorganic hybrid intrinsic polymers.
Disclosure of Invention
In order to overcome the defect of low thermal conductivity of the existing polymer-based material, the invention mainly aims to provide an organic-inorganic hybrid intrinsic liquid crystal epoxy resin.
The invention also aims to provide a preparation method of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.
The invention also aims to provide application of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.
Compared with the common epoxy resin structure, the organic-inorganic hybrid intrinsic liquid crystal epoxy resin structure has the advantages that the ordering and high-degree conjugate structure of the central liquid crystal element and the network structure formed by the Schiff base structure complexing silver provide effective channels for phonon transmission, the silver dispersibility is greatly improved compared with a silver/epoxy composite material, and the prepared organic-inorganic hybrid intrinsic liquid crystal epoxy resin has lower thermal resistance.
The purpose of the invention is realized by the following technical scheme:
an organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer has the following chemical structure:
wherein R1, R2, R3 can be selected from one of the following structural units, which can be the same or different:
wherein denotes the attachment position.
The preparation method of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer comprises the following steps:
(1) Synthesis of bisphenol structural intermediate: adding o-phenylenediamine, a catalyst, vanillin or o-vanillin or m-hydroxybenzaldehyde or p-hydroxybenzaldehyde or o-hydroxybenzaldehyde and a solvent into a reactor, and refluxing and stirring for 8-24 hours at 40-80 ℃; washing the solid obtained by the reaction, and then drying at 50-80 ℃ for 20-30 h to obtain a bisphenol structure intermediate;
(2) Synthesizing a liquid crystal type epoxy resin monomer: adding the bisphenol structure intermediate synthesized in the step (1), a solvent, a catalyst and epichlorohydrin into a reactor, reacting for 2-4 h at 70-90 ℃ in the atmosphere of nitrogen, cooling to 10-25 ℃, and adding 20-40% (w/w) of NaOH aqueous solution to continue reacting for 30-90 min; washing the solid obtained by the reaction, and then drying at 50-80 ℃ for 20-30 h to obtain a liquid crystal epoxy resin monomer;
(3) Adding the liquid crystal epoxy resin monomer obtained in the step (2) and a solvent into a reactor, then adding silver nitrate, stirring for 1-3 h, adding a reducing agent, reacting for 3-8 h at 25-60 ℃, adding water for recrystallization, and then drying for 20-30 h at 50-80 ℃ to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.
The organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer is applied to the preparation of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.
The preparation method comprises the following specific steps: and (3) taking the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, adding a curing agent, an accelerator and a solvent, removing the solvent in vacuum, removing bubbles, and then performing thermosetting to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.
The catalyst in the step (1) is preferably one of stannous chloride, glacial acetic acid and concentrated sulfuric acid; when the catalyst is a solid catalyst, the dosage of the catalyst is 2.5-5 wt% of the total reactants, and when the catalyst is a liquid catalyst, the dosage of the catalyst is calculated by adding 50-150 mu L of the catalyst per 100mL of the reaction system.
The molar ratio of the o-phenylenediamine to the vanillin or the o-vanillin or the m-hydroxybenzaldehyde or the p-hydroxybenzaldehyde to the o-hydroxybenzaldehyde in the step (1) is 1;
the solvent in the step (1) is acetonitrile or trichloromethane or absolute ethyl alcohol or N, N-dimethylformamide, and the dosage of the solvent is calculated according to the concentration of vanillin or o-vanillin or m-hydroxybenzaldehyde or p-hydroxybenzaldehyde or o-hydroxybenzaldehyde in a system of 0.2 to 0.5 mol/L.
The washing solvent in the step (1) is absolute ethyl alcohol or deionized water.
The epichlorohydrin is used in the step (2) according to the ratio of the bisphenol structure intermediate: epichlorohydrin = molar ratio 1.
The catalyst in the step (2) is tetrabutylammonium bromide or tetrabutylammonium chloride, and the dosage of the catalyst is 2.5-5 wt% of the total reactants.
The solvent in the step (2) is acetonitrile, N-dimethylformamide or dimethyl sulfoxide, and the dosage is controlled to be 0.2-0.4 mol/L according to the concentration of the bisphenol structure intermediate in a system.
The amount of the NaOH aqueous solution in the step (2) is preferably determined according to the bisphenol structure intermediate: naOH = molar ratio 1 to 2.
The using amount of the silver nitrate in the step (3) is calculated according to the molar ratio of the silver nitrate to the liquid crystal type epoxy resin monomer of 0.1-1, and the silver nitrate is prepared into a silver nitrate aqueous solution with the concentration of 1-2 mol/L by using deionized water before use.
The reducing agent in the step (3) is N, N-dimethylformyl, ascorbic acid or ethanol, and the using amount of the reducing agent is the same as that of the silver nitrate substance.
The solvent in the step (3) is acetonitrile, acetone or dimethyl sulfoxide, and the dosage is controlled to be 0.1-0.5 mol/L according to the concentration of the liquid crystal type epoxy resin monomer in the system.
In application, the curing agent is 4,4 '-diaminodiphenylmethane or 4,4' -diaminodicyclohexylmethane, and the dosage is calculated according to the molar ratio of the curing agent to the organic-inorganic hybrid liquid crystal epoxy resin monomer being 1.
In application, the accelerant is 2-ethyl-4-methylimidazole or 2-methylimidazole, and the using amount of the accelerant is 0.5-1 wt% of the total amount of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer and the curing agent.
In the application, the solvent is acetone or dichloromethane, and the dosage is controlled to be 2-2.5 mol/L according to the concentration of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer in the system.
In application, the heat curing conditions are as follows: 4,4' -diaminodiphenylmethane is adopted for curing at 120 ℃ for 3h, curing at 150 ℃ for 3h, and post-curing at 170 ℃ for 2h; or 4,4' -diaminodiphenylmethane is adopted for curing at 110 ℃ for 4h,155 ℃ for 3h and post-curing at 160 ℃ for 2h.
An organic-inorganic hybrid intrinsic liquid crystal epoxy resin is prepared by the method.
The organic-inorganic hybrid intrinsic liquid crystal epoxy resin is applied to the fields of electronic packaging materials and heat conduction.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention adopts the Schiff base structure to synthesize the liquid crystal epoxy resin with high planarization, and silver nano particles are synthesized in situ between mesomorphic elements based on the complexing effect of Schiff base and metal ions, so that the organic-inorganic hybrid high-thermal-conductivity liquid crystal epoxy resin is synthesized.
(2) The order of the resin can be effectively increased by introducing the Schiff base structure and in-situ synthesis of the silver nanoparticles, and in addition, the introduction of the silver can greatly reduce the interface thermal resistance of the resin matrix and provide an effective heat conduction network for phonon transmission.
(3) Compared with pure epoxy resin (0.19-0.21W m), the organic-inorganic hybrid high-thermal-conductivity liquid crystal epoxy resin prepared by the invention -1 K -1 ) The heat-conducting property of the material is greatly enhanced (0.7-1.6W m) -1 K -1 ) The thermal conductivity coefficient of the polymer is 3.7-8.4 times that of the traditional polymer matrix.
(4) Compared with pure epoxy resin (60-80 MPa), the tensile strength of the material is greatly enhanced and can reach 100MPa.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) 0.01mol of o-phenylenediamine, 0.02mol of vanillin, 50 mu L of glacial acetic acid and 100ml of acetonitrile are added into a three-neck flask with a condenser pipe, and the mixture is heated to 40 ℃ in a magnetic stirring oil bath kettle and refluxed for 8h. Then washing with water, and drying in a vacuum oven at 50 ℃ for 24h to obtain the bisphenol structure compound.
(2) In a three-necked flask under nitrogen atmosphere, 0.01mol of bisphenol structural intermediate, 2.5wt% of total reactants of tetrabutylammonium bromide, 0.04mol of epichlorohydrin and 50ml of acetonitrile were reacted at 70 ℃ for 2 hours, cooled to 10 ℃, and 2g of aqueous NaOH (20% (w/w)) solution was added to continue the reaction for 30 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at 50 ℃ to obtain the liquid crystal epoxy resin monomer.
(3) And adding 0.01mol of the liquid crystal epoxy resin prepared in the previous step and 100ml of acetonitrile into a single-neck flask in nitrogen atmosphere, then adding 10mL of 1mol/L silver nitrate aqueous solution, stirring for 1h, adding 0.01mol of N, N-dimethylformyl, reacting for 3h at 25 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 50 ℃ in a vacuum oven to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.
(4) 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4,4' -diaminodiphenylmethane, and 0.5 mass percent of 2-ethyl-4-methylimidazole based on the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent are added with 5ml of dichloromethane to be uniformly mixed, vacuumed and foamed for 10min, cured for 3h at 120 ℃, cured for 3h at 150 ℃ and cured for 2h at 170 ℃ to obtain the high-thermal-conductivity epoxy resin material.
The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the heat conductivity coefficient reaching 0.7W m -1 K -1 。
Example 2
(1) 0.01mol of o-phenylenediamine, 0.021mol of o-vanillin, 50 mu L of concentrated sulfuric acid and 42ml of N, N-dimethylformamide are added into a three-neck flask with a condensing tube, the temperature is raised to 50 ℃ in a magnetic stirring oil bath kettle, and the reflux is carried out for 12 hours. Then washing with water, and drying in a vacuum oven at 55 ℃ for 24h to obtain the bisphenol structure compound.
(2) In a three-necked flask under nitrogen atmosphere, 0.01mol of bisphenol structural intermediate, 3wt% tetrabutylammonium chloride, 0.05mol of epichlorohydrin and 50ml of N, N-dimethylformamide were added and reacted at 80 ℃ for 2.5 hours, cooled to 15 ℃, and 3g of NaOH (20% (w/w)) aqueous solution was added and the reaction was continued for 40 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at 55 ℃ to obtain the liquid crystal epoxy resin monomer.
(3) Adding 0.01mol of the prepared liquid crystal epoxy resin and 80ml of acetone into a single-neck flask in nitrogen atmosphere, then adding 30mL of a solution of 2mol/L silver nitrate, stirring for 1.5h, adding 0.006mol of ascorbic acid, reacting for 5h at 40 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 60 ℃ in a vacuum oven to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.
(4) 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4,4' -diaminodiphenylmethane, and 2-ethyl-4-methylimidazole with the mass fraction of 1 percent of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent are added with 5ml of acetone to be uniformly mixed, air is pumped in vacuum for 10min, the mixture is cured at the temperature of 120 ℃ for 3h, cured at the temperature of 150 ℃ for 3h and cured at the temperature of 170 ℃ for 2h to obtain the high-thermal-conductivity epoxy resin material.
The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the heat conductivity coefficient reaching 0.85W m -1 K -1 The tensile strength was 85MPa.
Example 3
(1) 0.01mol of o-phenylenediamine, 0.025mol of m-hydroxybenzaldehyde, 2.5wt% of stannous chloride and 80ml of trichloromethane are added into a three-neck flask provided with a condenser tube, and the mixture is heated to 80 ℃ in a magnetic stirring oil bath kettle and refluxed for 24 hours. Then washing with absolute ethyl alcohol, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain the bisphenol structure compound.
(2) 0.01mol of bisphenol structural intermediate, 5wt% tetrabutylammonium chloride, 0.08mol of epichlorohydrin and 50ml of N, N-dimethylformamide were added to a three-necked flask under nitrogen atmosphere to react at 80 ℃ for 4 hours, cooled to 18 ℃, and 2g of NaOH (40% (w/w)) aqueous solution was added to continue the reaction for 80 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at the temperature of 80 ℃ to obtain the liquid crystal epoxy resin monomer.
(3) Adding 0.01mol of the liquid crystal epoxy resin prepared by the method and 20ml of dimethyl sulfoxide into a single-neck flask in nitrogen atmosphere, then adding 10mL of 1mol/L silver nitrate solution, stirring for 3h, adding 0.01mol of ascorbic acid, reacting for 6h at 60 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 80 ℃ in a vacuum oven to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.
(4) 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4,4' -diaminodicyclohexylmethane and 2-methylimidazole with the mass fraction of 1 percent of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent are added with 5ml of acetone to be uniformly mixed, air bubbles are pumped in vacuum for 10min, the mixture is cured at 110 ℃ for 4h, cured at 155 ℃ for 3h and cured at 160 ℃ for 2h to obtain the high-thermal-conductivity epoxy resin material.
The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the heat conductivity coefficient reaching 1.2W m -1 K -1 The tensile strength was 70MPa.
Example 4
(1) 0.01mol of o-phenylenediamine, 0.023mol of o-hydroxybenzaldehyde, 4wt% of stannous chloride and 70ml of trichloromethane are added into a three-neck flask provided with a condenser tube, and the temperature is raised to 65 ℃ in a magnetic stirring oil bath kettle and the reflux is carried out for 24 hours. Then washing with absolute ethyl alcohol, and drying in a vacuum oven at 65 ℃ for 24h to obtain the bisphenol structure compound.
(2) 0.01mol of bisphenol structural intermediate, 3.5wt% tetrabutylammonium chloride, 0.1mol of epichlorohydrin and 40ml of N, N-dimethylformamide were added to a three-necked flask under nitrogen atmosphere and reacted at 90 ℃ for 3 hours, cooled to 25 ℃, and 2g of NaOH (30% (w/w)) aqueous solution was added and the reaction was continued for 90 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at the temperature of 80 ℃ to obtain the liquid crystal epoxy resin monomer.
(3) Adding 0.01mol of the prepared liquid crystal epoxy resin and 25ml of dimethyl sulfoxide into a single-neck flask in nitrogen atmosphere, then adding 35mL of aqueous solution of 2mol/L silver nitrate, stirring for 2h, adding 0.007mol of ascorbic acid, reacting for 8h at 50 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 80 ℃ in a vacuum oven, thus obtaining the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.
(4) 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4,4' -diaminodicyclohexylmethane and 2-methylimidazole with the mass fraction of 0.5 percent of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent are added with 5ml of dichloromethane to be uniformly mixed, air is pumped in vacuum for 10min, the mixture is cured at 120 ℃ for 3h, cured at 150 ℃ for 3h and cured at 170 ℃ for 2h to obtain the high-thermal-conductivity epoxy resin material.
The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the thermal conductivity coefficient reaching 0.92W m -1 K -1 The tensile strength was 92MPa.
Example 5
(1) 0.01mol of o-phenylenediamine, 0.024mol of p-hydroxybenzaldehyde, 5wt% of stannous chloride and 80ml of absolute ethyl alcohol are added into a three-neck flask provided with a condenser pipe, and the mixture is heated to 60 ℃ in a magnetic stirring oil bath kettle and refluxed for 24 hours. Then washing with absolute ethyl alcohol, and drying in a vacuum oven at 65 ℃ for 24h to obtain the bisphenol structure compound.
(2) In a three-necked flask under nitrogen atmosphere, 0.01mol of a bisphenol structural intermediate, 4wt% of tetrabutylammonium bromide, 0.06mol of epichlorohydrin and 50ml of N, N-dimethylformamide were reacted at 90 ℃ for 3 hours, cooled to 20 ℃, and 2g of an aqueous NaOH (20% (w/w)) solution was added to continue the reaction for 60 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at the temperature of 80 ℃ to obtain the liquid crystal epoxy resin monomer.
(3) Adding 0.01mol of the liquid crystal epoxy resin prepared by the method and 50ml of dimethyl sulfoxide into a single-neck flask in nitrogen atmosphere, then adding 10mL of aqueous solution of 2mol/L silver nitrate, stirring for 3h, adding 0.02mol of N, N-dimethyl formyl, reacting for 8h at 60 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 80 ℃ in a vacuum oven, thus obtaining the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.
(4) Taking 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4,4' -diaminodicyclohexylmethane, and 2-methylimidazole with the mass fraction of 1% of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent, adding 5ml of acetone, uniformly mixing, carrying out vacuum air suction for 10min, curing at 120 ℃ for 3h, curing at 150 ℃ for 3h, and curing at 170 ℃ for 2h to obtain the high-heat-conductivity epoxy resin material.
The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the heat conductivity coefficient reaching 1.6W m -1 K -1 The tensile strength was 100MPa.
Comparative example 1
The thermal conductivity of a common resin matrix is shown in table 1 below:
TABLE 1 thermal conductivity of conventional resin matrices
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. An organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer is characterized in that: the chemical structure is as follows:
wherein R1, R2 and R3 can be selected from one of the following structural units in an identical or different way:
h, wherein H represents a bonding site.
2. The method for preparing the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) Synthesis of bisphenol structural intermediate: adding o-phenylenediamine, a catalyst, vanillin or o-vanillin or m-hydroxybenzaldehyde or p-hydroxybenzaldehyde or o-hydroxybenzaldehyde and a solvent into a reactor, and refluxing and stirring for 8-24 hours at 40-80 ℃; washing the solid obtained by the reaction, and then drying the solid for 20 to 30 hours at the temperature of between 50 and 80 ℃ to obtain a bisphenol structure intermediate;
(2) Synthesizing a liquid crystal type epoxy resin monomer: adding the bisphenol structure intermediate synthesized in the step (1), a solvent, a catalyst and epichlorohydrin into a reactor, reacting for 2-4 h at 70-90 ℃ in a nitrogen atmosphere, cooling to 10-25 ℃, and adding 20-40% (w/w) NaOH aqueous solution to continue reacting for 30-90 min; washing the solid obtained by the reaction, and then drying at 50-80 ℃ for 20-30 h to obtain a liquid crystal epoxy resin monomer;
(3) Adding the liquid crystal epoxy resin monomer obtained in the step (2) and a solvent into a reactor, then adding silver nitrate, stirring for 1-3 h, adding a reducing agent, reacting for 3-8 h at 25-60 ℃, adding water for recrystallization, and then drying for 20-30 h at 50-80 ℃ to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.
3. The method for preparing the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 2, wherein:
the catalyst in the step (1) is one of stannous chloride, glacial acetic acid and concentrated sulfuric acid; when the catalyst is a solid catalyst, the dosage of the catalyst is 2.5 to 5 weight percent of the total reactants, and when the catalyst is a liquid catalyst, the dosage of the catalyst is calculated by adding 50 to 150 mu L of the catalyst into each 100mL of reaction system;
the molar ratio of the o-phenylenediamine to the vanillin or the o-vanillin or the m-hydroxybenzaldehyde or the p-hydroxybenzaldehyde to the o-hydroxybenzaldehyde in the step (1) is 1;
the solvent in the step (1) is acetonitrile or trichloromethane or absolute ethyl alcohol or N, N-dimethylformamide, and the dosage is calculated according to the concentration of vanillin or o-vanillin or m-hydroxybenzaldehyde or p-hydroxybenzaldehyde or o-hydroxybenzaldehyde in a system of 0.2 to 0.5 mol/L;
the washing solvent in the step (1) is absolute ethyl alcohol or deionized water.
4. The method for preparing the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 2, wherein:
the epichlorohydrin is used in the step (2) according to the ratio of the bisphenol structural intermediate: epichlorohydrin = mole ratio 1;
the catalyst in the step (2) is tetrabutylammonium bromide or tetrabutylammonium chloride, and the dosage of the catalyst is 2.5-5 wt% of the total reactants;
the solvent in the step (2) is acetonitrile, N-dimethylformamide or dimethyl sulfoxide, and the dosage is controlled to be 0.2-0.4 mol/L according to the concentration of the bisphenol structure intermediate in a system;
the amount of the NaOH aqueous solution in the step (2) is calculated according to the bisphenol structure intermediate: naOH = molar ratio 1.
5. The method for preparing the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 2, wherein:
the use amount of the silver nitrate in the step (3) is calculated according to the molar ratio of the silver nitrate to the liquid crystal type epoxy resin monomer of 0.1-1, and the silver nitrate is prepared into a silver nitrate aqueous solution with the concentration of 1-2 mol/L by using deionized water before use;
the reducing agent in the step (3) is N, N-dimethylformyl, ascorbic acid or ethanol, and the using amount of the reducing agent is the same as that of the silver nitrate substance;
the solvent in the step (3) is acetonitrile, acetone or dimethyl sulfoxide, and the dosage is controlled to be 0.1-0.5 mol/L according to the concentration of the liquid crystal type epoxy resin monomer in the system.
6. Use of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 1 for preparing an organic-inorganic hybrid intrinsic liquid crystal epoxy resin.
7. Use according to claim 6, characterized in that:
the preparation method comprises the following specific steps: taking the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer of claim 1, adding a curing agent, an accelerator and a solvent, removing the solvent in vacuum, degassing bubbles, and then carrying out thermal curing to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.
8. Use according to claim 7, characterized in that:
the curing agent is 4,4 '-diaminodiphenylmethane or 4,4' -diaminodicyclohexylmethane, and the dosage is calculated according to the mole ratio of the curing agent to the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer of 1;
the accelerant is 2-ethyl-4-methylimidazole or 2-methylimidazole, and the using amount of the accelerant is 0.5 to 1 weight percent of the total amount of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer and the curing agent;
the solvent is acetone or dichloromethane, and the dosage is controlled to be 2-2.5 mol/L according to the concentration of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer in the system;
the heat curing conditions are as follows: 4,4' -diaminodiphenylmethane is adopted for curing at 120 ℃ for 3h, curing at 150 ℃ for 3h, and post-curing at 170 ℃ for 2h; or 4,4' -diaminodiphenylmethane is adopted for curing at 110 ℃ for 4h, at 155 ℃ for 3h and at 160 ℃ for 2h.
9. An organic-inorganic hybrid intrinsic liquid crystal epoxy resin is characterized in that: prepared by the process as claimed in claim 7 or 8.
10. The organic-inorganic hybrid intrinsic liquid crystal epoxy resin as claimed in claim 9, which is used in the fields of electronic packaging materials and thermal conduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011470779.5A CN112625215B (en) | 2020-12-15 | 2020-12-15 | Organic-inorganic hybrid intrinsic liquid crystal epoxy resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011470779.5A CN112625215B (en) | 2020-12-15 | 2020-12-15 | Organic-inorganic hybrid intrinsic liquid crystal epoxy resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112625215A CN112625215A (en) | 2021-04-09 |
| CN112625215B true CN112625215B (en) | 2022-12-27 |
Family
ID=75313110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011470779.5A Active CN112625215B (en) | 2020-12-15 | 2020-12-15 | Organic-inorganic hybrid intrinsic liquid crystal epoxy resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112625215B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5265461B2 (en) * | 2008-07-16 | 2013-08-14 | 新日鉄住金化学株式会社 | Crystalline modified epoxy resin, epoxy resin composition and crystalline cured product |
| CN104962037A (en) * | 2009-02-25 | 2015-10-07 | 松下电器产业株式会社 | Thermoconductive composition, heat dissipating plate, heat dissipating substrate and circuit module using thermoconductive composition, and process for production of thermoconductive composition |
| CN111205594A (en) * | 2018-11-21 | 2020-05-29 | 苏州巨峰先进材料科技有限公司 | Preparation method of epoxy resin-based composite material with high-thermal-conductivity ordered structure |
-
2020
- 2020-12-15 CN CN202011470779.5A patent/CN112625215B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112625215A (en) | 2021-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107434905B (en) | heat-conducting polymer composite material and preparation method and application thereof | |
| CN109206853B (en) | High-thermal-conductivity epoxy resin-based composite material, and preparation method and application thereof | |
| CN102875973B (en) | Modified carbon nanotube/thermosetting resin composite and preparation method thereof | |
| CN108659467B (en) | Method for compositely modifying epoxy resin by SiC/graphene oxide | |
| CN111777841B (en) | Lamellar anisotropy-based graphene/epoxy resin composite material and preparation method thereof | |
| CN114031943B (en) | Inter-surface high-thermal-conductivity composite material and preparation method thereof | |
| CN115572486B (en) | Heat-conducting insulating polymer material composite film based on boron nitride filler and preparation method thereof | |
| CN111777840A (en) | Epoxy resin micro-nano blending composite material for packaging power electronic high-power device and preparation method thereof | |
| CN113043680A (en) | High-heat-dissipation aluminum-based copper-clad plate | |
| CN112625215B (en) | Organic-inorganic hybrid intrinsic liquid crystal epoxy resin and preparation method and application thereof | |
| Li et al. | Flexible and thermally conductive epoxy‐dispersed liquid crystal composites filled with functionalized boron nitride nanosheets | |
| CN115260575B (en) | Heat conduction framework with vertical orientation and preparation method and application thereof | |
| CN112048199A (en) | Computer mainboard heat dissipation coating and preparation method thereof | |
| CN114015238B (en) | Insulating heat-conducting gasket containing COF coated carbon fiber and preparation method thereof | |
| CN113416384B (en) | CNTs @ CC heat-conducting filler and heat-conducting composite material based on same | |
| CN111793363B (en) | Annual ring-shaped graphene organic silicon resin bionic composite material and preparation method and application thereof | |
| CN113789055A (en) | MOFs modified BT nano composite material containing transition metal and active hydrogen and preparation method thereof | |
| CN109503889B (en) | Preparation method of silver nanowire hybrid filler and composite material using filler | |
| CN114369335A (en) | Heat dissipation plate for IGBT and preparation process thereof | |
| CN117659621A (en) | Epoxy resin-based composite material and preparation method and application thereof | |
| CN110240892A (en) | A kind of bionic laminar graphene/imide derivative thermally conductive film and preparation method thereof | |
| CN113121961B (en) | MFS @ CNT epoxy resin composite material and preparation method thereof | |
| CN117567346B (en) | Bismaleimide and preparation method thereof, and method for preparing aviation heat-resistant die plate | |
| CN113549296A (en) | Epoxy resin high-thermal-conductivity composite material and preparation method thereof | |
| CN110117760A (en) | A kind of preparation method of high thermal conductivity continuous fiber Cf/Cu composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 512400 No.3, Ping'an 1st Road, Zhuji Industrial Park, Nanxiong City, Shaoguan City, Guangdong Province Patentee after: Shaoguan Institute of new materials Patentee after: Guoke Guanghua fine chemical incubator (Nanxiong) Co.,Ltd. Patentee after: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Patentee after: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd. Address before: 512400 No.3, Ping'an 1st Road, Zhuji Industrial Park, Nanxiong City, Shaoguan City, Guangdong Province Patentee before: GUANGZHOU CHEMICAL INSTITUTE SHAOGUAN TECHNOLOGY INNOVATION AND BREEDING CENTER, CHINESE ACADEMY OF SCIENCES Patentee before: NANXIONG CAS INCUBATOR OPERATION CO.,LTD. Patentee before: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Patentee before: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd. |